DE2166141A1 - INDICATOR DYES - Google Patents

Description

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Ί ΐ.ί-ΐ- tj ιϊλ M M t :: i'A .. 'Κ "Γ WW λ I T i;." ι »ηοί ι: * - γι λτι: λ · τ μ Γμ · ι- <'.. \

IA »41 892

3 e S ο hre ibu η g KU of the file confirmation message

POLAROID CORPORATION 'JjO Main Street, Cambridge, Massachusetts, USA 021 39

concerning:

Indicator dye a

The invention relates to special indicator dyes, whose area of application is in photo technology. They are characterized by special light absorption in such areas, that they can be used as an optical filter medium for color photographic materials. This optical Filter means serve to protect selectively exposed photographic recording materials from accidental Exposure to incident light during non-dark development.

According to the invention it was found that certain indicator dyes, derived from phenol or benzophenol,

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e.g. naphthols, are very suitable as optical filter media, around exposed photosensitive material before fogging due to post-exposure in the context of photographic applications Process to protect in which the photosensitive Material after the selective exposure and thus build-up of the latent image and during the first Time of development is exposed to non-selective external light. In the case of the phenol indicator dyes under discussion are those that have a ring-closing unit bonded to two hydroxy-substituted, contain carbocyclic aryl radicals, the latter having two p-hydro: cyphenyl groups, each containing one hydrogen bonding group, adjacent to the p-hydroxy group, and two p-hydroxynaphthyl radicals are present, at least one of which has a hydrogen-bonding group, adjacent to the p-hydroxy group.

As shown by pH-Vert sensitive dyes in general these phenolic indicator dyes have spectral properties that are reversibly alterable with change the surrounding pH. They have a strongly colored form, which in an alkaline medium at a 1. pH value, the is above its pKa value, an absorption in the visible Spectrum show and can be in an essentially colorless manner In form, i.e. in a form in which they are substantially non-light absorbing within the visible Spectrum 'at a less alkaline second pH value, which is below its pKa value. Under the term pKa value is understood as the pH value at which about 50% of the dye in the light-absorbing form and about 50% is in the non-light absorbing form.

Aside from their color-changing behavior, these

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se dyes a \ I have other properties that they -appear particularly useful within phototechnilc permit. Your pKa value is in such a range that they can be used in conventional photographic processes which are generally carried out in an alkaline medium are. This applies to both shell development and diffusion transfer and other processes, where development is carried out at a relatively high pH value. The dyes are in their colored form able to absorb radiation in the longer wavy range of the visible spectrum, depending on the dye chosen, to prevent photographic material from fogging by post-exposure within to protect the green and red parts of the spectrum. A highly effective light-absorbing system over the entire visible spectrum, i.e. over about 400 and 7oo nn to achieve, one can use the phenol dyes according to the invention together with other optical filter means, such as other dyes that have their effective absorption in the shorter wavy range, that is in the blue part of the spectrum have to apply.

Due to its pKa vert and the spectral absorption in Associated with the ability to be light-absorbing or non-light-absorbing by suitable adjustment of the surrounding pH to be, these phenol-derived dyes are particularly useful in photographic processes using multi-part film units, the measures for. Include changes in ambient pH, in particular Diffusion Transfer Process (U.S. Patent 3 4-15,644 and U.S. Pat. 786 352, 43 782 and 101 968).

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2166H1

As already indicated above, it has been found according to the invention, that _t a selectively exposed photosensitive material containing a latent image in the presence of externally incident actinic radiation can be developed because a sufficient protection of the invention for .the longer wavelength region of the visible spectrum by the Indicator dyes, which are derived from the phenols, is guaranteed. These dyes fall under the general formula:

where A ° and B ° are p-hydroxynaphthyl and / or p-hydroxyphenyl radicals, in the case of the naphthyl radical, at least one should have the grouping:

OH

cry, in which one of the cubic substituents, JR ¹ , R ^{2 is} a water-

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the other is a substance-binding group is. The hydroxyphalyl radicals contain the foundation:

• 5 ο

where R is a hydrogen bonding group and X is the atoms required to complete the ring-closing unit, this being a phthalide or naphthalide, provided that the phthalide having a carboxy group in at least one of the 4- or 7-positions is when A is ⁰ and B ^{0 are} p-hydroxyphenyl radicals.

If A and B are p-hydroxynaphthyl radicals, preference is given Substances in which R is a hydrogen bonding group and the second p-hydroxyphenyl group of the formula:

OH

corresponds to where R can be a hydrogen bonding group, the same as or different from R.

In contrast to the 1-naphtholphthalides and -naphthalides,

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which generally have good stability in an alkaline medium, it was found that the phenol indicator dyes, containing 'as a ring-closing unit' a naphthalide, show good stability in aqueous alkalis, while indicator dyes, which have a simple, i.e. an unsubstituted phthalide group as a ring-closing unit tend to lose their color very quickly in an alkaline and strongly alkaline environment. It was determined, that phenolphthalide indicator dyes in alkalis can be stabilized like the naphthalides by substitution with a carboxy group in the 4- and / or 7-position of the phthalide ring system.

It was also found that the pKa of the phthalides and naphthalides of phenol and 1-naphthol, i.e. the pKa value, the the color causes can be increased by substitution of the hydrogen bonding group on the Phenol and 1-IIaphthol residues. In particular, the Increased pKa-Vert of 1-laphtholphthalides and -naphthaLides are obtained by substituting one of the p-hydroxynaphthyl radicals with a hydrogen-bonding group on a carbon " adjacent to the p-hydroxy group. Both p-hydroxynaphthyl radicals are attached to a hydrogen-bonding group, this shows a further increase in the pKa value. The pKa values of phenolphthalides and naphthalides increase by substitution of hydrogen-bonding groups on both naphthol radicals in o-position to the p-hydroxy group. The indicator dyes obtained can be due to their colored form at a higher pH as an optical filter medium in photographic processes use to protect from selectively exposed light-sensitive! Material from incident actinic radiation in the longer term Wave range of the visible spectrum.

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2166H1

In the above formulas, any hydrogen-binding groups can be used to increase the pKa values of the substances. The association of two atoms via hydrogen with the formation of a so-called hydrogen bond between or within molecules is known. If the hydrogen atom is attached to an electronegative atom, such as oxygen or nitrogen, the bond that enters is polarized.If it is directed towards another atom (M) with an unseparated electron pair, the hydrogen atom acts as a bridge between these atoms (0-H. ..11) due to the electrostatic attraction of the two atoms, between which the proton can be shifted. According to the invention, an intramolecular hydrogen bond is formed between the p-hydroxy group and the adjacent hydrogen-bonding group, i.e. a group containing a heteroatom which has an active, unseparated electron pair, such as oxygen, nitrogen, sulfur or halogen, e.g. fluorine, which is a free one Has a pair of electrons or a negative charge in alkaline solution and is able to form 5-, 6- or 7-membered, preferably 5- or 6-membered, hydrogen-bonded rings with the p-hydroxyl group. In a preferred embodiment, the heteroatom in the hydrogen-bonding group is linked to a proton which is more acidic than the proton of the phenolic or naphtholic hydroxyl group and ionizes to a negative charge in alkaline solution. Examples are the carboxy, hydroxy, o-hydroxyphenyl group, bis-trifluoromethylcarbinol, sulfonamido group (-HH-SO ₀ -R ⁰ , where R ° can be an alkyl, aryl or alkaryl group) and the sulfamoyl group (-SCU -NH-R where R can be an alkyl, aryl or alkaryl group). The substituents R, R ¹ can be straight-chain or branched

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chain alkyl groups, e.g. methyl, ethyl, isopropyl, η-butyl, t-3utyl, hexyl, octyl, dodecyl, hexadecyl, Octadecyl and eicosanyl groups, aryl groups such as phenyl and naphthyl groups and alkaryl groups such as benzyl, Phiethyl, phenylhexyl, p-octylphenyl and p-dodecylphenyl groups.

If it is desirable for the indicator dye to be essentially immobile or non-diffusible in the developing or processing solution, compounds with sulfamoyl or sulfonamido substituents have the advantage of being immobilizable together with the hydrogen-binding function in the sulfonamido and sulfamoyl substituents (-NH- SO ₂ -R ⁰ or -SO ₂ -NH-R ¹ ) * contain the immobilizing substituents R, R ¹ , such as the hexadecyl or p-dodecylphenyl group.

Compounds according to the above general formula can also carry further substituents in addition to the hydrogen-binding ones Groups on, one or both of the residues and / or the ring-closing moiety, e.g., solubilizing groups for Improvement of the solubility of the indicator dyes in certain developer compounds, or immobilizing groups, if the indicator dye in the developer composition is to be made essentially non-diffusible, or also other hydrogen-binding or other groups for setting the desired pKa value for certain Development conditions. Finally, there may be other substituents, such as alkyl groups, that do not interact with the photographic functions of the indicator dyes in their application as optical filter media, present, such as branched or straight-chain alkyl groups, aryl groups and alkaryl groups, such as benzyl, phen

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ethyl, phenylhexyl and p-dodecylphenyl groups and alkoxy groups, like methoxy-, ethoxy-, butoxy-, 1-ethoxy-2- (ß-äthoy.yäthoxy) - or octadecyloxy groups, finally aryloxy groups, v; ie phenoxy, benzyloxy and naphthoxy, also alkoxyalkyl groups, such as methoxyethyl, ethoxyethoxyethyl and dodecyloxyethyl groups; In addition, halogen atoms such as fluorine, bromine or chlorine can also be used, Sulfo groups, carboxy groups, hydroxyl groups and amino groups including 1- and 2-times substituted amino groups, such as N-alkylamino and H, N'-dialkylamino groups. These Substituents can be present on one or both radicals and / or also occur in the ring-closing unit.

Finally, there may also be substituents in the form of a condensed ring system. For example, one or both radicals can represent a cycloaliphatic or aromatic ring with 5 or 6 members and be carbocyclic or heterocyclic, optionally substituted and bonded to the adjacent carbon atom, such as:

OH

and

OH

wherein R ^{0 is,} for example, a hydroxyl group.

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The dyes according to the invention show this combination of properties, namely 1. effective absorption of actinic radiation within the wavelength range from about 500 to 700 nm, 2. high pKa value, namely 11 and above, 3. stability - in a highly alkaline medium and optionally 4 «not diffusing in aqueous alkalis.
These dyes fall under the formula:

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HO

(II),

where E is a hydrogen-bonding group with a negative charge in alkaline solution and X ^{1 is} the atoms required to complete the ring-closing unit in the form of a phthalide or naphthalide, the latter being substituted by a carboxy group in at least one of the 4- and 7-positions.

The ring-closing naphthalides and carboxyphthalides of the Formulas:

and

have a carboxyl group as at least one of the ßubstitu-

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2Ί66141

U-41

ten H ^f? ,

on.

(Ill)

With reference to formula Ia it is pointed out that the phenol dyes of the formula II and the 1-naphthol ~ dyes of the formula III are new indicator dyes. The dyes of the formula II are phenol dyes Formula Ia, the substances of the formula III are preferred Dyes from the group of the 1-naphthol dyes general formula Ia.

As in the formula I, the substances of the formulas II and III can contain further substituents which do not affect the photographic function as an optical filter medium, such as solubilizing groups, e.g. carboxy and SuIfοgruppen, or immobilizing groups, such as long-

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chain alkyl groups or other voluminous groups which can be cyclic or acyclic and which make the indicator dyes essentially non-diffusible in the course of development. As already mentioned above, one will not use a separate immobilizing group in addition to the hydrogen-binding group, but rather the immobilizing puncture is combined with the hydrogen-binding puncture by selecting an appropriate substituent, such as a sulfonanido or -SuKamoyl group, their substituents R °, R ^{1 are} a long chain alkyl group or other bulky group. For the substances of the formulas II and III, further substituents can also be present on the phenol or 1-naphthol radicals and / or the ring-closing unit.

Examples of the inventive dye developer as an optical filter medium are given below. The substances of the formulas 10 to 24 and 29 to 32 is new phenolic dyes, which under the general formulas Ia and fall II, whereas the substances of the formulas 33-56 Examples of new 1-naphthol of general formula I and III .

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-H-

1A-4't

(D

HO

OH. OH

(2)

COOH

COOH

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216514.1

1A-41 B

(4)

SO ₀ -NH- f ° 2 -NH- Ήο-τ ίίΊ -OH CH ₃ -I -CH ₃ " ^C 12 ⁿ 2S

(5)

CH (CH ₃ )

HO

CH-SO ₂ -HN CH (CH ₃ )

OH

NH-SO ₂ -CH ₃

(6)

NE-SO ₂ -C ₈ H ₁₇ NH-SO ₂ -C ₈ H ₁₇

H (CK ₃ )

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(7)

(8th)

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216614

UH '392

,-OH

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(13)

^H 25 ^C i2 (14)

^C 12 ^H 25

(15)

~ ^C 12 ^H 25

HO -.

CH (CH) 3 ^; 2

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-1S-

1-41

ΓΌΗ

EO

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1Δ-41 Ö92

(19)

(20)

COOH CH.

: ooH

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1A-41

^H 33 ^C 16 °

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OH

COOH

KH-SO ₃ -C ₃ H _7-

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1A-41

OE

HOOC HOOC

HOOC

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(30)

(31) (32)

- 24 -

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OH

COOH

OH OH

PH OH

COOH

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U-41

OH OH

OH OH

HOOC

COOH

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n- ^H 33 ^C 16 °

HOOC

- ^ 309815/1023

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(39)

(40)

(41)

e ^COOH

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(42)

(43) CF ₃ -C

CF

OH OH

COOH

COOH

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(45)

COOH

(47)

^H 25 ^C 12 " ^SO 2- ^HN 309815/1023

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(48)

OH OH

COOH

H ₇ C ₃ -NH-SO ^

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SO ₂ -NH-C ₃ H ₇

(51) H-C, - SO _n -NH OH

1A-41

(52)

CF ₃ -C-OH

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(54)

⁽⁵⁵⁾

(56)

NH-SO ₂ '

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(57)

(58)

COOH

^H 25 ^C 12

~ ^<: 12 ^Η 25 ·

COOH

COOH

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2166H1

(60)

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(61)

OH

(62)

HOOC 309815/1023

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(63)

OH OH

(64)

(65)

HOOC

0OH

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Various processes can be used to produce the indicator dyes according to the invention the phenol or naphthol _t of a catalyst such as a tiewis'sehen acid at an elevated temperature in the presence of.

Another method of making the phthaleins is by reacting the phenol or naphthol with phthalaldehydiurei Naphthalaldehyde or carboxyphthalaldehyde in the presence of a mild acidic catalyst, such as p-toluenesulfonic acid, so that the correspondingly substituted intermediate is formed, which is obtained by treatment with dichlorodicyanoquinone or another oxidizing agent is oxidized.

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The oxidized intermediate is then implemented with a other aromatic compound, which can be a phenol or a naphthol, in the presence of an acid catalyst, whereby the desired dye is synthesized. Through this process, both the symmetrical and the asymmetric indicator dyes by appropriate selection of the second aromatic compound as pheno] or naphthol, which may be the same or different from the starting phenol or naphthol, which is in the first stage was reacted with the aldehyde acid. . This process for the preparation of the phenolphthaleins and Naphtholphthaleins as well as those of the aromatic chosen Compounds derived phthaleins is the subject of another application (USA application 108,662 of January 21, 1971)

This process takes place in the following process stages:

1) A hydroxy-substituted carbocyclic aryl compound with -a vacancy para to the hydroxy group in Fora a phenol or a 1-naphthol is reacted with an N-heterocyclic aryl compound whose heteroatom is substituted by hydrogen, in the form of an indole with a free 3-position or a pyrrole with a free 2-position with phthalaldehyde acid or naphthalaldehyde acid forming a substance of the formula:

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U-41

wherein C is a p-hydroxyphenyl, p-IIydroxynaphthyl-, indolyl- or pyrryl-2 group and X 'those to complete the ring-closing unit required carbon atoms for the phthalide or /. Represent naphthalide.

2) This compound is oxidized to

and or

OH

where C is the groupings:

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and

are and C and X ^{1 have} the above meaning,

3) Reaction of the oxidation product with an aromatic one Compound in the form of a carbocyclic or heterocyclic substance to form the indicator dye the formula:

C.

where D is derived from the carbocyclic or heterocyclic aromatic and C and X ^{1 have} the above meaning.

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Ira following is only for the sake of simplicity nor of phthalide, phthalaldehyde and phthalaldehyde acid Spoken, but it is also used accordingly Caphthalide, naphthalaldehyde and naphthalic acid Understood.

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To carry out the above process, the starting materials are reacted at room temperature or at an elevated temperature in a solvent, namely the hydroxyl-substituted carbocyclic or N-heterocyclic compound with the phthalaldehyde acid. In some cases, this process is preferably carried out in the presence of an external acid catalyst, for example an organic acid such as toluene-p-sulfonic acid, trifluoroacetic acid or trichloroacetic acid. The reaction temperature can vary and is generally between room temperature di about 20 ⁰ C, and elevated temperature in the order of about 120 ° C, the most suitable reaction temperature can be easily selected for the Realctionspartner determined. In order to achieve reaction rates that are acceptable in practice, the reaction will probably be carried out at elevated temperatures, but decomposition or side reactions with the formation of by-products will be prevented. Any inert organic liquid solvent can be used, such as glacial acetic acid, ethanol, propanol, petroleum ether, hexane, heptane, cyclohexane, toluene, methylene chloride or benzene. Normally a polar solvent will be chosen if an acid catalysis laboratory is used and a non-polar solvent if the reaction is carried out without a catalyst.

The phthalidyl intermediate of phenol, naphthol, indole or pyrrole is oxidized by splitting off hydrogen from the 3-position of the phthalidyl radical UDd from the hydroxyl group of phenol or naphthol or from the nitrogen atom of the indoles or pyrroles, the single bond of the two parts of the molecule in a double bond transforms. The are particularly suitable for this purpose

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Quinones, e.g. ο- or p-quinones, * v / ie dicyandichloroquinone, Chloranil or o-chloranil. These substances selectively split off the hydrogen atoms in the desired manner, but without further oxidizing the compounds. Any organic liquid can be used as the solvent for the oxidation stage, which is compatible with the Oxidizing agent does not react, v / ie dioxane, toluene, benzene, Dichloroethane or hexane. The temperature can vary over a wide range and is generally between about 20 and 200 ° C. As is the case with the first condensation stage the oxidation stage preferably at elevated temperature carried out in the. In view of the fact that no by-products should be formed, can be easily determined.

Now a second aromatic compound is condensed on the oxidation product and the indicator dye _{N is} formed. This second condensation reaction can, like the first, be carried out in a solvent at room temperature or elevated temperature, preferably in the presence of an acid catalyst, such as phosphorus oxychloride, boron trifluoride (e.g. in benzene or ether) or with a Lewis acid such as zinc chloridej or countless others above mentioned catalysts, v / ie p-toluenesulfonic acid, trifluoroacetic acid, trichloroacetic acid. An inert organic solvent can be used in all of these customary condensation reactions, as already mentioned in the context of the first condensate "ion reaction".

The starting materials are preferably used in equimolar amounts. The same applies to the quantity parts of oxidizing agents and the phthalidyl intermediate, however, it is preferred to use a small excess of oxidizing agent in order to bring the reaction to completion.

¹⁰ · ^{] 1ί}

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It has thus been found that a molar ratio of oxidizing agent to intermediate product of 1.1 to 1.5 * 1 is satisfactory is * also in the second condensation between the oxidized intermediate and the second aromatic compound equiinolar ones are preferably used for the synthesis of the dye Shares in

All phenols or 1-naphthols can be used as starting materials be applied with the hatred that they have a free ^ position own, "that is, in the p-position to the phenolic Hydroxyl group are unsubstituted This ensures that that a hydrogen shift on the first condensation with the acid to a 4-phthalidyl intermediate product leads. Likewise, all indoles or pyrroles can be used as starting material with the proviso that they have a free 3-position or 2-position, whereby in the first condensation reaction, the corresponding 3-phthalidylindoles or 2-phthalidy! pyrroles are obtained will come. The indoles and pyrroles should be a free one 1-position, i.e. the nitrogen atoms should only have Be substituted with hydrogen.

Apart from the positions that must be kept free, the starting materials can have one or more substituents, which are desired in the indicator dyes contain, provided that the substituents are blocked next to the condensation site with a tendency to bond internally with the dehydro intermediate and the blocking groups become after condensation of the intermediate with the second aromatic compound remove, e.g. the carboxy group of 2-carboxyindcl can be protected as an alkyl ester and the blocking alkyl group becomes alkaline after synthesis of the dye

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Split off hydrolysis. ₁ Similarly, a nydroxylsubntituierto aryl or alkyl ~ ^ roup in the 2-position on the indole protected as alkyl ethers v / ground. The protective group is then removed during the catalytic splitting off of hydrogen.

The clear numbering of the carbocyclic and N-heterocyclic Compounds that serve as starting materials can, emerges from the following formula images:

OH

OH

The ones used to react with the hydroxyl-substituted carbocyclic or N-heterooyclic compounds Phthalaldehyde acids can be substituted, for example they can carry carboxy groups, such as 4-carboxyphthalaldehyde acid and 7-carboxyphthalaldehyde acid; can also use suIfonftfiido groups substituted substances are used, e-Hexadecylsuifonaaido-naphthalaldehyde acid.

The aromatic compound to be used for the condensation with the oxidized intermediate product can be a carbocyclic aryl compound of the benzene or naphthalene series or a heterocyclic aryl compound with oxygen, metal, sulfur and / or phosphorus. Preferred as the heterocyclic !! - heterocyclic compounds, such as indoles,

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Pyrroles, carbazoles and those derived from N-benzylindoline applied _i.

The following is the preparation of some of the inventions Dyes explained in more detail.

Production example 1

For the " preparation of the substance of the formula 13-

a) 7.68 g (0.04 mol) of hemimellitic anhydride and

4.73 g (0.04 mol) of zinc chloride were stirred into 9.41 g (0.1 mol) of phenol in a 100 cc three-necked flask on an oil bath and heated to 150 ° C. under nitrogen with stirring. The dark purple solution was stirred for 20 h, abrekühüb to 90 ⁰ C and 50 cc of water was added excess Fhenol was removed by steam distillation, back "thief an off-white precipitate. This was dissolved in 100 cc of a 5% sodium hydroxide solution and filtered .. The alkaline solution was acidified with 10% hydrochloric acid until the purple color disappeared. The white precipitate was filtered off, dried and recrystallized, giving 9.6 g (67% by weight yield) of phenol-7-carboxyphthalide in the form of white crystals (melting point 246 ⁰ C).

b) 5 g (0.015 mol) of the above substance were dissolved in * 100 ecm acetic acid in a three-necked flask with nitrogen supply and magnetic stirrer in an ice bath, the solution was cooled to 18 to 20 ° C and 1.9 g (0.031 mol) nitric acid ( 70%) in 3 ecm acetic acid was added dropwise over 10 min. The yellow solution was allowed to warm to 26 ° C. and was then stirred for a further 2 h. The reaction mass was poured into 150 ecm of ice with stirring, the yellow lower

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blow filtered off, dried and from ethyl acetate-Hcxan recrystallized. 5.4-5 G (oil 1% of the yield) were obtained o-nitrophenol-carboxy-phthalide, melting point 250 ° C.

c) 2.26 g (0.005 mol) of this "substance were in 25 ecm
Ethanol and 100 ecm Dichlonnethan dissolved, 0.5 S carbon with palladium catalyst (5 fr) added and that
shaken for 17 hours. After the theoretical amount of hydrogen had been absorbed, 3.88 g (0.01 mol) of p-dodecylbenzenesulfonyl chloride were dissolved in 50 ecm of acetone and 3.95 g of pyridine were added under a stream of nitrogen, the reaction mixture was shaken at room temperature for 14 h and the brownish solution was removed of the catalyst filtered and
200 ecm of ethyl acetate were added to the filtrate. The ethyl acetate solution was washed with 5% hydrochloric acid, dried over magnesium sulphate, filtered and evaporated. The brown, gummy residue was taken up in dichloromethane and chromatographed in a column filled with silica gel. After elution with dichloromethane containing 3 % acetone, 1.15 g (22 % yield) of the desired substance were obtained as white crystals.

Production example 2

For the preparation of the compound of formula 14.

a) Following the steps in Example 1, 51.8 g (0.48 mol) of freshly distilled o-cresol with 38.4 g (0.2 mol) of heiaimellitic anhydride in the presence of 27.2 g (0.2 mol)
Zinc chloride implemented. 43.6 g of o-cresol-7-carboxyphthalide, melting point 280 ° C. with decomposition, were obtained.

b) 24.3 g (0.062 mol) of the above substance were in 350 ecm
Acetic acid with 70% nitric acid in an HSn ^ e of 12.6 g

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(0.14 mol) implemented. 26.4 g of the corresponding were obtained o-Hit'ro connection. Melting point 2-7 ° C.

c) 1.68 g (0.0035 mol) of the above o-nitro compound were dissolved in 25 ecm of ethyl acetate and 25 ccra \ dichloromethane, and the catalyst (5 % palladium on carbon) was introduced, shaken for 16 h, with 18 kg Hydrogen, after the theoretical amount of hydrogen had been absorbed, 2.5 g (0.0072 Hol) of p-dodecylbenzenesulfonyl chloride in 37 ecm of acetone and then 2 ccai of pyridine were introduced. The reaction water was under for 12 h. Shaken nitrogen at 26 ° C., treated with 20% strength methanol-dichloromethane on silica gel, the amine indicator formed as an intermediate product, obtained by hydrogenation, disappeared, and the sulfonide product was formed. The brownish reaction solution was filtered and 200 ecm of ethyl acetate was added. The solution was washed with 5% hydrochloric acid, dried over magnesium sulfate, filtered and evaporated.

The brownish-orange-colored residue was dissolved in dichloromethane added and one working with dichloromethane on silica gel Column abandoned. After elution with dichloromethane and 3% acetone-dichloromethane were the most diverse Eliminates impurities. By increasing to 5% acetone dichloromethane the product was removed. The product solution was evaporated to a yellow glassy residue which was taken up in sufficient dichloromethane. The product was precipitated with "hexane, filtered off, dried, one obtained 1.138 g of an off-white solid, melting point 94-96 ° C.

Production example 3

For the preparation of the compound of formula 31

4 g of aluminum trichloride were 6 g of a solution of biphenol

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15 ecm in tetrachloroethane were added with stirring, the solution was heated to refluxing boiling and then 2.5 g of 3.3 dichloronaphthalide in 1 o ecm tetrachloroethane were added dropwise over a period of about 1 hour. The red solution was refluxed overnight and then poured hot onto ice water. A yellowish gummy mass separated out, which was steam-distilled, the cooled mixture of gum-like solid and water was distributed between water and chloroform, the aqueous extract was discarded, the chloroform extract was washed neutral with water, dried on an oily substance, this was taken up in 1 of the above sodium hydroxide solution (75 ecm), the blue-pure-pure solution filtered and acidified. The gummy solid formed was taken up in chloroform, washed, dried and concentrated to a brown oil. The oil was placed in a column operating with "Florisil" (highly selective magnesium silicate gel for adsorption chromatography) and chloroform. Some impurities were eluted with chloroform. The product was removed by elution with 5 i ° methanol-chloroform and then eluted again over a Plorisil column with chloroform. All fractions were collected, dried and the brown oil was dissolved in about 100 ecm of dichloroethane. The white solid was filtered off and dried. Melting point 225 to 226 ⁰ C.

Production example 4

To prepare the compound according to formula 3o

The production took place in the sense of Example 1 by reacting biphenol and hemimellitic anhydride.

Production example 5

For the preparation of the compound according to formula 29

The production took place in the sense of Example 1 by

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setting of Bi phenol with Hellithsäuretrianhydrid Herste!

For the preparation of the compound nacli- Formula 10

The production was carried out in the sense of Example 1 Implementation of pyrocatechin with hemimellitic anhydride.

Since "the dye product according to Example 1 c) in the form of amino phenol carboxyphthalein and according to Example ?. C) Amino-o-cresol-carboxyphthalein were not isolated before reaction with p-dodecylbenzenesulfonyl chloride, this can happen if mixed.

If in the sense of z.3. Example 1 Hemimellitic anhydride applied, a mixture of two isomers is obtained, namely phenol-4-carboxyphthalide and -7-carboxyphthalide, which, if desired, are separated chronographically can. Phenol-7-carboxy-phthalide can also be used before the first separation from the reaction mixture Recrystallization. (Example 1) win.

Because of the ring-closing unit in the form of liaphthalids or curboxyphthalids, phenol indicator dyes in the sense of the formulas Ia and II have good stability in the alkaline environment Milieu .. The improved alkali stability is shown by the fact that the dyes also exist in strong aqueous alkalis Keep color. To demonstrate this, the dyes were used dissolved in 2m hydroxide solution and the color spectrophotometrically Determined immediately after mixing and after 10 minutes to determine if on standing discoloration takes place.

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Such comparisons show that biphenolphthalein decolorizes very quickly in strong alkalis and has less than 1.5 color after 10 minutes. The biphenolcarbox3 / phthalein or naphthalein dyes obtained according to Examples 3 and 4 still had a color content of 100 % after 10 min (the biphenolphthalein was obtained in the sense of Example 1a by reacting biphenol with hemellitic anhydride).

As already indicated above, the phenol have indicator dyes according to the formulas Ia and II, relatively high pKa values of about 11 and above in addition to their good resistance to im alkaline medium. Such are the pKa values for phenol-7-carboxyphthalein and phenol-4-carboxyphthalein at about 9.6. In comparison, the values for pyrocatechol -? - carboxy-phthalein (Formula 10), o-dodecylbenzenesulfonamidophenol-7-carboxy-phthalein (Formula 13), o-dodecylbenzylsulfonamidocresol-7-carboxyphthalein (Formula 14) and biphenyl-7-carboxyphthalein (Formula 30) 11.2 and 12.8 and 12.9 and 13i4, respectively. It also turned out that Biphenolnaphthalein (Formula 31) compared to a pKa value> 15 has a pKa value of 9.7 for phenolnaphthalein.

Production example 7

Preparation of the compound according to formula 39

a) 50 g (0.266 mol) of dry 1-hydroxy-2-naphtholic acid were in 350 ecm of dry benzene in a 1 liter Eund-. flask suspended with air condenser and drying tube. 31.7 g (0.266 moles) of thionyl chloride were added all at once and then subsequently 1.5 ecm of dry N, N-dimethylforrraraid. The reaction mass was stirred magnetically for 2 to 3 days at room temperature, 6.5 g of insoluble substances

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filtered off, the yellow-brownish filtrate evaporated to dryness; nan received pale yellow i-IIydroxy-2-naphthoyl chloride, Melting point 87-88 ° G. It quickly became 100 ecm cold anhydrous methanol added. One followed exothermic reaction, the partial solution was about 5 rain in the steam bath heated under a drying tube and then allowed to cool. The suspension was quenched, the solid won. 43 g (92% yield) of 1-hydroxy-2-methylnaphthoate were obtained. ■

b) 30.2 6 (0.149 mol) of the naphthoate were in 400 ecm Dissolved dry 1,1,2,2-tetrachloroethane in an Erlenmeyer flask with a drying tube, and the solution was cooled on an ice bath and anhydrous aluminum chloride (84 g, 0.625 moles) were carefully added in portions. After about 1/3 of the Catalyst was added, a violent evolution of hydrogen chloride took place, so that the further addition faster could be done. 100 ecm of nitrobenzene were then added to the cooled dark green suspension and the mass temporarily stirred until a strong brown solution was obtained. This could then be used for about 1/2 hour stand.

37.8 g (0.149 mol) of 3,3-dichloronaphthalide were in 100 ecm 1 »1,2,2-tetrachloroethane in a 2 l three-necked flask with Dropping funnel, air condenser, mechanical stirrer and Dissolve the drying tube, cool the solution in an ice bath, decant the previously prepared complex solution in the dropping funnel and dripped into the well-stirred reaction liquid within $ 0 to 60 minutes. It developed immediately a strong purple color. The reaction mass was stirred and could then stay overnight at room temperature.

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300 to 5 ¹ OO pounds of excess ice were carefully removed. solid reaction liquid was added and then 20 ecm concentrated hydrochloric acid was introduced. The dropping funnel and the condenser were exchanged ge.gen a Claisen still, with the help of which the organic solvents were distilled off under steam. A yellowish brown crude product was obtained from the hot, dilute acid. It was allowed to air dry overnight.

It was completely dried in vacuo, the dry solids were taken up in hot glacial acetic acid (approx. 1 g to 10 ecm), the insoluble product was filtered off, the ketol crystallized out when left to stand, and this was then dried. Traces of impurities were removed by dissolving in hot toluene (about 1 g in 5 ecm). A yield was obtained from about 50 to 60 wt. -Γο of 3-hydroxy-3-. (3'-carbonethoxy-V-hydroxynaphthyl) -naphthalide-1,8.

c) A solution of an equivalent liaphthalide above and three equivalents of 1-caphthol in dry acetic acid were made (about 1 g on 15 ecm). It now became a Equivalent boron trifluorate added and the reaction mixture boiled under reflux for several hours. The precipitated solid was washed with ether and then with hydrolyzed hot methanolic sodium hydroxide solution. The desired product had a melting point of 277 to 279 ° C.

Production example 8

For the preparation of the compound according to formula 4-9

a) A mixture of 3.6 g of diisopropylethylamine and 5.6 g n-propylamine was added dropwise to 7.3 g of 1-carbomethoxynaph-

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Thalin-I-sulfonyl chloride in 2 % of chloroform and kept at 50 ° to 6 ° C. for a further 15 minutes. It also formed a precipitate. Further rain was warmed up, whereupon the solution was cooled, acidified with hydrochloric acid and the chloroform chased away. The residue was recrystallized 3 times from benzene-hexane, giving about 4.5 g of 2-n-propylsulfamoyl-i-naphthol (melting point 61 to 64 ° C.).

b) 2.4 g of this intermediate product and 1.8 g of naphthalaldehyde acid were dissolved in 50 ecm acetic acid and 30 ecm of a 12% acetic acid solution of p-toluenesulphonic acid were added. The whole could remain under refluxing overnight. The reaction mass was then poured into an equal volume of cold water, the precipitate collected and recrystallized from benzene-petroleum ether. 3 g were obtained, melting point 189 to 191 ^° C.

c) 50 ecm of a 10% sodium hydroxide solution was flushed with nitrogen for 2 h and then 2.3 g of the product obtained in process stage b) and 1.4 g of the product obtained in process stage a) were introduced. The solution was kept C overnight at 60 °, then heated to 70 ⁰ C and kept at this temperature for about a 48th The reaction mass was then cooled, the pH was adjusted to about 1 with dilute hydrochloric acid, and the precipitate formed was collected, washed and taken up in benzene. The benzene solution was treated with activated charcoal, filtered, concentrated until a precipitate formed, this was collected. 2.5 g of a white pesticide, melting point 178 to 180 ° C., with decomposition were obtained.

d) 710 mg of the product obtained in process step c) were dissolved in 30 ecm of dimethylformamide and 230 mg of sodium

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hydrid 57> ÜS added, the solution until the end of the Hydrogen evolution kept at 80 ° C, whereupon 470 mg of silver oxide added and the whole thing at Raun temperate was stirred overnight. It was then another 8 hours warmed to 8ü ° C, the reaction mass then filtered, the filtrate poured into 30 ecm of water with dilute hydrochloric acid acidified and the precipitate collected. This was then taken up in benzene and chronographed on silica gel. Elution with 10% ethyl acetate in benzene gave about 100 mg of the desired compound.

Production example 9

Preparation of the compound according to formula 4-5

Two equivalents of the indicator dye obtained according to Preparation Example 7 were dissolved in 1 g (5 ecm) of ethanol in a three-necked round bottom flask equipped with a stirrer, thermometer and dropping funnel. 2.5 equivalents of n-dodecylamine dissolved in 1 g (10 ecm) of ethanol were introduced all at once into the reaction vessel. The well-stirred solution was added over 1 h treated dropwise with a Forinalinlösung in ethanol (about 1.5 equivalent of formaldehyde in 1 CCRN / 5 cc of ethanol) was added such that the temperature of the reaction mass did not exceed 3O ⁰ C. The mass was stirred at room temperature for several hours, then filtered, washed with ethanol and then evaporated. The residue was washed with hexane to remove unreacted dodecylamine.

The arain-substituted intermediate was in dry Pyridine (1 g / 10 ecm) in a round bottom flask with a dropping funnel Dissolved in an ice bath at about 5 ° G. Then 5 equivalents of acetyl chloride were added dropwise, after the addition the cooling

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bath removed so that the reaction mixture could warm to room temperature. It was then poured into dilute hydrochloric acid, the solid collected, dissolved in methanol (1 g / 40 ecm) and filtered. Then dilute caustic was added and gradually. Stirring for about 1 hour, the precipitate is collected, washed, dried and recrystallized from ethyl acetate / hexane.

Preparation example 10 For the preparation of the compound according to formula 44

»') 50 B (0.125 mol) 3-hydroxy-3- (3'-carbomethoxy-4 ^l -hydroxynaphthyl) -naphthalide-1,8, suspended in 500 ecm dry benzene, were in a 1 liter round bottom flask with magnetic stirrer and Calcium sulfate drying tube with 16.4 g (0.137 mol) of thionyl chloride and then with 2.5 ecm of dry Ν, Ν-diraethylfornamide. The suspension was stirred for 1 day * at room temperature, the precipitated 3-chloro-3- (3 ^l -carboaethoxy-4'-hydroxynaphthyl) -naphthalide-1,8 was filtered off on a Buchner funnel and washed with small amounts of dry hexane. The remaining solvent was removed in the vacuum excicator.

b) 20.6 g (0.106 mol) of freshly prepared silver tetrafluoro © borate were weighed into 900 ecm of dry dioxane and 40 g (0.088 mol) of 1-hydroxy-6-octadecyloxy-2-nephthalic acid were introduced into this slurry. The reaction took place with good stirring under a nitrogen atmosphere. Then 55.4 g (0.132 mol) were added to the produced in process step a) pseudo chloride, brought the whole ton ~ ückfließenden Siedln. A dark purple color appeared as the reaction progressed, while silver chloride precipitated at the same time. After 2 to 3 hours of boiling on the back

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Flux were further 5.8 ε (0.02 ΓΙοΙ) silver tetrafluoroborate added and refluxed for a further 14 hours. Then 10 ecm of water were carefully poured into the hot Mixture introduced, the whole cooled to room temperature and over a cushion of the filter aid "Celit" (on a silica basis) filtered. The brown filtrate was "brought to dryness"

Vr cumEle residue treated with 100 ecm boiling benzene. After cooling the benzene, the solid was filtered, the benzene filtrate was evaporated in vacuo and the gumai-like

"Residue in 50 to 60 ecm boiling absolute ethyl alcohol solved. This solution was allowed to stand for a few hours, then it was filtered, and 7 g of the desired product were obtained. The filtrate was concentrated to half volume, allowed to stand overnight, leaving about 2 g of unreacted Acid contaminated with a small amount of the reaction product obtained. This filtrate was evaporated, the residue dissolved in 50 to 60 ecm of glacial acetic acid and after standing overnight, a further 8.4 g of the desired product was obtained Product. All of the portions of the product were recrystallized from about 200 ecm of glacial acetic acid to obtain 11.4 g of the half-ester in the form of a gray-white solid, melting point 230 to 232 ° C.

<0.5 »5 g (6.55 mmol) of the half-ester were in 250 ecm dissolved in warm dioxane and diluted with 150 ecm of ethanol.

250 ecm of 3% potassium hydroxide solution were added to the solution, the deep blue solution was kept on the steam bath for 2 to 3 hours, during which the color of the reaction mass was deep green became. The solution was then cooled to room temperature, acidified with 10% hydrochloric acid with vigorous stirring.

The brown gunmiartice precipitate was off after several hours solidified sufficiently that it could be filtered.

After recrystallization from glacial acetic acid (about 1 c / ^ 00 con)

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4.8 g of the desired white solid, melting point 263 to −5 ° C.

The 1-hydroxy-6-octadccyloxy-2-naphtholic acid used in process stage b) was prepared by adding 67.4 g (1.35 mol) of sodium methoxide to a solution of 1C0 g (0.625 mol) of 1,6-dihydroxy naphthalene. in 900 ecm dry N, N-dimethylformamide, saturated with dry carbon dioxide. A steady stream of carbon dioxide was passed through during the reaction. About 125 ecm of the dimethylformamide distilled off. The mixture was then refluxed for 15 minutes to remove an additional 125 ml of solvent. The solution was then cooled and the flow of carbon dioxide turned off. The reaction mass was then acidified with concentrated hydrochloric acid and poured onto about 2 kg of ice. The dark precipitate was filtered off and dried and treated with 1 liter of boiling benzene. The dark impurities were filtered off and, after recrystallization from water gave as' .reißen solid 1,6-dihydroxy-2-naphthoic acid, mp 220-221 ⁰ C.

The well-stirred slurry of 5.1 g (0.025 mol) of 1,6-dihydroxy2-naphtholic acid in 50 ecm of dry isopropyl alcohol was mixed with 5.65 g (0.05 mol) of potassium t-butoxide under nitrogen, all for Brought to refluxing boiling and stirred for 10 to 15 Elin, before 8.35 g (0.025 mol) of octadecyl bromide were added. The reaction was continued under reflux for 5 hours, the whole thing was cooled and acidified with 20% strength hydrochloric acid. The precipitate was filtered off, dried and recrystallized from absolute ethanol. 3.8 g of a gray precipitate were obtained. Through further recrystals it is ti nn rmo

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form "one received 2.3 G of i-Hydroxy-ö-octadecyloxy - ^ - naphtholic acid as. white solid, melting point 164 to 165 ° C.

Preparation example 11

For the preparation of the compound according to formula 43

A mixture of 0.84 g (2 mmoles) of 3-chloro-3- (3'-carbomethoxy-4'-hydroxynaphthyl) -naphthalide-1,8, 0.62 g (2 mmoles) of 2- (bis-trifluoromethylcarbinol ) -i-naphthol and 0.4 g (2 mmol) of silver tetrafluorate in 75 ecm dioxane were refluxed for 4 h , 1 ecm V / water was added to the warm mixture and then filtered through a "Celite" filter aid. The filtrate was evaporated in vacuo, the gummy residue was dissolved in about 25 ecm hot benzene and the whole thing was cooled. 1 g of precipitate was obtained, which was recrystallized from a mixture of 2 ecm of chloroform and 25 ecm of benzene. 0.8 g of solid was obtained, melting point 260 to 262 ^° C. with decomposition. 0.5 g of this solid was dissolved in 10 ecm hot ethanol and this solution was added to 100 ecm 15% potassium hydroxide solution. The deep blue solution obtained was kept on the steam bath for 2 hours, cooled to room temperature and acidified with 20% hydrochloric acid. The whole thing could stand for several hours , a microcrystalline powder was then obtained in an amount of 0.35 Si, melting point 227 ° C.x with decomposition.

• Production example 12

For the preparation of the substance according to formula 41

A mixture of 0.42 g (0.001 mol) 3-chloro-3- (3'-carbomethoxy-4'-hydroxynaphthyl) naphthalide, 0.2 g (0.001 mol) methyl-1-

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hydroxyr-8-naphthoate and 0.2 g (0.001 mole) of silver tetrafluoa borate in 40 ecm of dioxane were refluxing sura for 5 h Boiling heated. The solution then filtered, water added, the solution evaporated to dryness and several sharks with Methanol azeotropically distilled. The residue was dissolved in petroleum ether / ethanol and the whole thing was cooled. Of the Precipitated pesticide was collected and dissolved in 12 ecm 25% sodium hydroxide solution and 36 ecm ethanol. The solution was heated on the steam bath for 30 min, then cooled with concentrated hydrochloric acid acidified, the ethanol chased off and the solid taken up in ether after filtering off. The ether solution was filtered, evaporated to dryness and treated with petroleum ether. The petroleum etlier was chased away, the desired compound was obtained, melting point 206 ° to 210 ° C. with decomposition.

Preparation example 13

For the preparation of the compound according to formula 42

2 g of .3-Hydroxy-3 - (. 3 ^l -carbomethoxy-4'-hydroxynaphthyi) -naphthalide-1,8 were suspended in 250 ecm of anhydrous methanol and the suspension was saturated with dry hydrogen chloride gas. Most of the solid dissolved into a brownish solution. This was heated under refluxing for 30 min, cooled and the solvent removed in vacuo. The residue was treated with ether and filtered; after recrystallization from chloroform-isopropanol, 1.5 S 3-methoxy-3- (3'-carbomethoxy-4'-hydroxynaphthyl) naphthalide, melting point 232 to 233 ° C., was obtained with decomposition.

1.5 g of this naphthalide, 1.2 g of 6-dodecyloxy-i-naphthol and 0.8 g of boron trifluoride etherate in 100 ecm of benzene were over

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Boiled under reflux overnight, then evaporated the reaction mixture to dryness, on the steam bath with methanol-petroleum ether heated ', filtered the deposited solid, boiled in isopropanol and ^ filtered again. so the solid was dissolved in tetrahydrofuran and extracted with 6% sodium hydroxide solution (20 ecm). The organic one The extract was extracted by shaking with 20% hydrochloric acid, sodium chloride and dichloromethane were added, and then the solution dried over magnesium sulfate and finally evaporated to dryness. The residue was made from benzene / isopropanol recrystallized to the desired product.

Manufacturing example 14

For the preparation of the substance according to formula 40

528 mg of 3-hydroxy-3- (3 ^l -carbomethoxy-4'-hydroxynaphthyl) -naphthalide-1,8, 480 mg of 2-hexadecyl-1-naphthol and 184 g of boron triuride etherate in 12 ecm of glacial acetic acid were refluxed for 3 h, the solution cooled and concentrated to half volume. The precipitate which formed on standing was recrystallized from ethanol.

A solution of 0.8 g of this solid in 25 ecm of ethanol was treated with 5 ecm of a 10% strength sodium hydroxide solution, heated for 2 hours in the steam bath, the reaction mass was cooled and acidified with 20% strength hydrochloric acid. The gummy precipitate ¹ was rubbed with water and digested until completely solidified. Then it was air dried, dissolved in boiling cyclohexane. A white solid immediately precipitated out of the hot solution. 0.5 g of the desired substance, melting point 214 to 215 ° C., was obtained.

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Herstallurr-nbej £; t> jc1 15
"For the preparation of the substance according to formula 35

57, G 6 (0.2 col.) 1-hydroxy-2-naphtholic acid and 20.3 g '(0.1 mol) 3 »3 -dichlorophthalide are dissolved in ether with warming, the solution is cooled and 23 ecm ( 0.2 mol) of tin chloride was added dropwise, the whole thing was stirred at room temperature for about 48 hours, after which the ether was evaporated. A green oil was obtained, the addition of ethanol turned the solution pale pink and a white pesticide precipitated. This was filtered off, sodium hydroxide solution was added until the reaction was basic, the alkali-insoluble residue was filtered off, the filtrate was acidified with acetic acid, the pale pink precipitate obtained was filtered off and dissolved in alkali. The material, which was insoluble in alkali, was filtered off, and the filtrate was acidified with acetic acid, as a result of which a precipitate reappeared. These measures are repeated until a purple solid is obtained on acidification. This was placed in a column filled with silica gel and this was eluted with dichloromethane containing 1% methanol, the proportion of which was increased to 10%. At 20 % methanol, most of the product was removed. The fractions containing the product were combined and evaporated to give 350 mg. After recrystallization from 50 ecm hot 2-methoxyethanol, a light purple precipitate was obtained, melting point 273 to 275.degree

Example of manufacture 16

For the preparation of the compound according to formula 34

10 g (0.049 mol) of the methyl ester of 8-hydroxy-i-naphtholic acid, 2.3 ecm (0.016 mole) phthaloyl chloride and 5.8 ecm

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(0.05 mole) Zdnnchlorid vrurden at 110 G ⁰ zusammenporührt and could etv; a to react for 2 hours. The dark brown, viscous reaction substance was poured into the ice vascer without cooling, the solid obtained was comminuted and taken up in a water / water / chloroform mixture. The organic phase was washed well with water and then dried for chromatography in a column operating on "Florisil" with chloroform. ^ The chloroform eluate served to remove some yellow impurities, further elution with chloroform led to the removal of alkali-soluble products. This fraction was suspended in 100 ecm of ethanol under nitrogen, and the suspension was treated with 6% sodium hydroxide solution (100 ecm) under nitrogen on a steam bath for 30 minutes. Ethanol was then evaporated off, leaving a green solution which was cooled with ice and adjusted to a pH of 5 with 10 ^ hydrochloric acid. An orange-brownish solid precipitated out, which was filtered off, washed with water and dried. Yield 2.3g, mp 165-168 ° C. The cloudy filtrate was extracted with ethyl acetate, 0.1 g of the solid was still obtained, which was combined with the above.

2.7 g of the material obtained as described above were treated with ethanol and the ethanol-insoluble solid was discarded. The ethanol solution was evaporated to a sticky mass, and then ^it was added strength sodium bicarbonate solution in 5%. The insoluble material was discarded and the bicarbonate solution was acidified with glacial acetic acid. The precipitate was filtered off, washed with warm water and dried. About 0.7 6 of a brown solid was obtained, which was taken up in methanol / benzene 1: 4-. The whole thing could stand overnight and then had separated into a dark brown oil and a light yellow supernatant liquid. The solvent was

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1A-41

standing liquid removed and hydrolyzed the remaining yellow Ul. The "brown solid was then dissolved in about 3 cc of glacial acetic acid, was some Iiinuten stand, the solution was then filtered to yield an off-white solid which was dried at 100 ⁰ C, melting point 212-213 ° C,

As already mentioned above, indicator dyes are obtained which are colored at higher pH values when one or preferably both p-hydroxy-naphthyl radicals with. one hydrogen bonding group are substituted. Through this Property, these dyes are particularly useful as optical filter media in phototechnology. 1-naphtholphthalein has a lower pKa value of 7 in comparison to the substances according to the formulas 34 and 35 with their plia values of 8.5 and 12.5, respectively. Note also the low pKa vert of 1-naphtholnaphthalene of about 8.5 compared to the dyes according to the invention according to the formulas 41, 39 and 44, which values of 9 »8 and 12.8 and 13.9 (1-naphtholnaphthalein was produced in the sense of Example 15 by implementing 1-naphthol with 3,3-dichiornaphthalide in the presence of tin chloride).

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The class of dyes listed above is capable of emitting radiation absorb within the longer wavelength range of the visible spectrum, at certain pH ranges within of the alkaline environment. They are usually soluble in developer solutions and have no adverse effect on usual developer and / or the latent image, which by selective exposure of the photosensitive material, e.g., a silver halide emulsion. The invention Phenolic dyes of the formulas II and III are particularly suitable in photographic processes involving strongly alkaline Use developer compounds with a pH of 12 and above. They are preferred in such procedures because of their good qualities Stability in a strongly alkaline environment. The phenolic dyes are essentially non-fogging, non-discoloring and non-toxic. Although in a preferred embodiment the phenolic dyes in developer compositions with initially alkaline chemical pH value can be included at which the dyes are able to absorb incident radiation and the developer composition is located in a destructible container, the dyes can also be permeable to developer in any desired Layers of the composite film unit between the photosensitive layers to be protected from incident radiation and the surface of the film unit over which the exposure takes place. If they are initially in one layer of the film unit, so should they at an ambient pH value at which the substances are essentially non-incident radiation before the ßelective Ability to absorb exposure of the film unit are present. Activation only takes place in contact with the alkaline developer, which penetrates this layer and thus creates a surrounding pH range in which the Means capable of absorbing the incident radiation and thus the light-sensitive silver halide emulsion layer able to protect against fogging during development.

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Claims (5)

DH. INtJ. F, WÜESTJIOFF DB-Kt. FKOUM ANN DJl. ING. B. BEUHENS DIPT «ING, K. GOKTZ PATiNTAMWlI-TE 46 "- 8 MUNt) IUiN OO * <08ii) on uo si TMUTtX 8 U * 070 TSt-BOIIAMMKI! • BOTJfOTPATKHT 1A-41 892 Claims Indicator dyes of the general formula wherein Α · and Β ° are p-hydroxynaphthyl radicals, of which at least one is the grouping 1 2
contains, in which R ¹ and R a hydrogen-bonding group and the other is a Y / asserstoffatom iat, or p-Hydroxyphenylreste, both the grouping 309815/1033 1A-41 892 are, wherein R ^ is a hydrogen bonding group, and X ° the for Completion of the ring-forming unit for a phthalide or naphthalide required atoms, provided that the Phthalide is substituted with a carboxy group in at least one of the 4- or 7-positions if A ° and B ° are p-hydroxyphenyl radicals are. 2. ζ e i Indicator dyes according to claim 1, characterized in that g e k e η n- c h η e t that both groups A " p-hydroxy are naphthyl radicals, in particular with a hydrogen-binding one 2 1 Group as a substituent R and a hydrogen atom as R. 3. Indicator dyes according to Claim 1 or 2, characterized marked A ° that the grouping OH and B ° are. 4. Indicator dyes according to claim 3j, characterized in that the substituents R and / or R are a carboxy group or SuIfamoy! Group. 5. indicator dyes according to claim 1, characterized in that both groups A ° and B ° are p-hydroxyphenyl, especially their substituent R ^ a sulfonamide, an o-hydroxyphenyl or a hydroxyl group is. . .,. · ~ 81XX 3U98TS / 1Ö23